Compositions for finishing textiles

ABSTRACT

Preparations for finishing textiles, more especially sheet-form textiles, based on emulsion polymers of vinyl acetate and/or copolymers thereof with dibutyl maleate containing protective colloids in addition to small quantities of standard auxiliaries, wherein the polymer emulsions contain as a protective colloid polyethylene glycol having an average molecular weight of from about 3000 to 50,000 which was at least partly present during the original emulsion polymerization.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to preparations for finishing textiles, particularly sheet-form textiles.

2. Statement of Related Art

It is known that sheet-form textiles can be finished by the application of aqueous emulsion polymers to the textile material to be finished. These auxiliaries applied in the course of finishing serve, inter alia, as filling agents, as stiffening agents, as non-slip agents, as weighting agents, as agents for improving seam tear resistance, as antisnagging agents, and the like. The plastic dispersions or emulsions used are, in particular, products based on vinyl acetate, dibutyl maleate, vinyl propionate, and acrylates. These products are also used to vary feel; polyvinyl acetate dispersions giving a very hard, stiff feel. Although feel can be improved by using plasticizers, this technical solution is seriously limited. The plasticizers are at least partly volatile at the temperatures used in various stages of the finishing process, so that the textile material undergoes an undesirable change in feel. Dibutylphthalate is one example of a platicizer of this type.

It is known that the deficiencies of vinyl acetate homopolymers plasticized in this way can be overcome by using copolymers of vinyl acetate with dibutyl maleate (DBM). Polyvinyl propionates used as finishing agents also give a softer and fuller feel than vinyl acetate homopolymers. Particularly full and soft feels are obtained where polyacrylate emulsions or dispersions are used. For economic reasons, however, it is desirable to use as large a quantity as possible of vinyl acetate or homopolymers and/or copolymers therof. As a particularly inexpensive component by comparison with all other potentially suitable monomers, vinyl acetate is rated particularly highly for the formation of the textile finishing preparation.

DESCRIPTION OF THE INVENTION

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".

An object of the present invention is to improve the known emulsion homopolymers and/or copolymers based on vinyl acetate and copolymers thereof with dibutyl maleate (DBM) to such an extent that, when used as textile finishing preparations, they have considerable advantages over comparable homopolymers or copolymers of the hitherto known type. They are intended in particular to give the textile a softer and fuller feel than hitherto known corresponding emulsion polymers based on vinyl acetate or copolymers thereof with DBM.

The invention is based on the surprising discovery that the choice of a specific protective colloid for emulsion polymers of the above type leads to the desired effects of increased fullness and greater softness in the feel testing of the resulting finished textiles.

Accordingly, the present invention relates to preparations for finishing textiles, more especially sheet-form textiles, based on emulsion polymers of vinyl acetate and/or copolymers thereof with DBM containing protective colloids in addition to small quantitive of standard auxiliaries, the new preparations containing as protective colloid in the polymer emulsions polyethylene glycol having an average molecular weight of from 3000 to 50,000, and which was at least partly present during the original emulsion polymerization process. The polyethylene glycol is preferably used in its entirety as a protective colloid during the original emulsion polymerization of copolymerization process.

Through the use of the above polyethylene glycol as a protective colloid, it is possible to produce polyvinyl acetate homopolymers and copolymers which, in the field of application of textile finishing preparations, are distinguished by a distinctly softer feel of the treated textile than where the usual protective colloids, for example polyvinyl alcohol and/or cellulose derivatives, are used. Another considerable advantage is that the dispersions used in accordance with the invention have a very high shear stability which benefits the processing of the dispersions in important steps of the textile finishing process. Through the optimization of those parameters of the preparations according to the invention which affect softness and feel, more especially the dibutyl maleate content and the quantity and type of protective colloid selected, within the framework indicated, it is possible to obtain products which, when applied to textiles, the superior to polyvinyl propionate dispersion with respect to the softness of the resulting feel. At the same time, however, these products satisfy all other requirements, particularly in regard to solids content, viscosity, dilutability, friction resistance and film quality. The possibilities for use of the present particularly inexpensive textile finish are thus considerably broadened.

The polyethylene glycols used as protective colloids are preferably present in a quantity of from 2 to 10% by weight, based on the total weight of the preparation. The content of vinyl acetate polymer or copolymer in the aqueous polymer emulsion is preferably from 40 to 60% by weight. Where copolymers of vinyl acetate with DBM are used, the DBM content may be up to 50 mole %, based on the sum of vinyl acetate and DBM, DBM contents of from about 5 to 45 mole % being particularly preferred. In general, the softness and fullness of the textile feel is greater or higher, the higher the DBM content of the copolymer.

The aqueous polymer dispersions of the invention also contain the usual auxiliaries in small quantities, including in particular emulsifiers, buffers, initiators for the polymerization reaction and/or salts. The emulsion polymers preferably contain no more than 5% by weight of these standard auxiliaries, and preferably from 0.5 to 3% by weight of emulsifiers. Suitable standard emulsifiers are, especially those based on nonionic surfactants, more especially polyethylene oxide adducts with hydrocarbon compounds containing a reactive hydrogen atom: preferred emulsifiers being alkylphenol-EO adducts. One example of a nonionic surfactant which makes a particularly suitable emulsifier is nonylphenol×10 EO. However, other nonionic surfactants with a modified EO chain are also suitable. Particularly appropriate quantities for the nonionic surfactant are from 0.5 to 2% by weight. Particularly suitable quantities for the polyethylene glycol present as protective colloid are from 3 to 10% by weight, polyethylene glycols having an average molecular weight of from 8000 to 25,000 being particularly suitable.

The preparation of a number of vinyl acetate homopolymers and copolymers used in accordance with the invention is first described in the following Examples which show important production parameters for these polymer emulsions. The emulsions according to the invention are then compared with 4 comparison emulsions which have been prepared in the absence of polyethylene glycol as protective colloid. In each case, the assessment of shear stability, as determined by roller application using the padding process, is shown in the description of the product. Shear stability is assessed as follows:

The dispersions are applied to a fabric by means of a laboratory padder. To this end, the dispersions are introduced undiluted into the trough of a padding machine, the lower roller dips into the dispersion, and the contact pressure of the upper roller is adjusted to 10 kp/cm. The shear stability of the dispersion is observed over a period of 30 minutes at a speed of 30 m/minute. If, after 30 minutes, there are no deposits to be seen on the upper roller and the lower roller shows a uniform film without any breaks, the friction resistance is assessed as very good. If no changes occur in the first 10 minutes, the mark "good" is awarded. If deposits are to be seen on the upper roller or breaks in the film on the lower roller within the first 6 seconds, the product is assessed as poor.

The invention will be illustrated but not limited by the following examples.

EXAMPLES A. Process for preparing the emulsion polymers or copolymers (a) Preparation on a laboratory scale

The apparatus used was a 2 liter capacity face-ground glass apparatus equipped with a metal anchor stirrer, an intensive cooler and metering vessels. Most of the water was introduced into the reaction vessel and the sodium carbonate, the emulsifier, the foam inhibitor--if any--and the protective colloid were dissolved therein over a period of 2 hours at 80° to 85° C. The monomers were introduced into a 0.5 liter metering funnel. To prepare the initiator solution, potassium persulfate was dissolved in cold water. The solution was introduced into another metering funnel.

To carry out polymerization, monomer and initiator solution were simultaneously introduced into the reaction vessel at 82° to 88° C. The monomer and initiator solution were added as shown in Table 1 below:

                  TABLE 1                                                          ______________________________________                                         Time     Initiator solution added                                                                       Monomer added                                         (mins.)  (ml)            (ml)                                                  ______________________________________                                          0        0               0                                                    20       20               52                                                   40       20              100                                                   60       35              170                                                   120      50              300                                                   180      65              425                                                   240      75              525                                                   ______________________________________                                    

The reaction was carried out with stirring (140 r.p.m.). The reaction temperature was kept between 80° and 88° C. In the event of excessive reflux, the addition of monomer was temporarily reduced. After addition of the monomer, the rest of the initiator solution was rapidly added. When the reflux had finished, the after-reation took place over a period of 30 minutes at 85° to 95° C.

(b) Preparation of dispersions on a 120 kg scale

The apparatus used was a 200 liter enamel apparatus with a capacity of 120 kg, an infinitely variable impeller stirrer, a 20 liter metering vessel and an ascending reflux condenser. The stirrer was adjusted to a speed of 140-200 r.p.m. After each batch, the apparatus was rinsed with water and then acetone and dried.

Procedure

Most of the aqueous phase was introduced into the reactor and sodium bicarbonate, emulsifier, foam inhibitor and protective colloid were dissolved therein over a period of 2 hours at 75° C. (preliminary solution). The intended quantity of monomer or the mixture of monomers was introduced into the metering vessel.

The initiator (potassium persulfate) was dissolved in the remaining water and the solution introduced into another metering vessel.

To carry out the polymerization, monomer and initiator solution were simultaneously introduced into the reactor at 82° to 88° C. at the rates shown in the following Table.

                  TABLE 2                                                          ______________________________________                                         Time     Initiator solution added                                                                       Monomer added                                         (mins.)  (1)             (1)                                                   ______________________________________                                          0       0               0                                                      20      1.86            6.3                                                    40      1.86            6.3                                                    60      3.46            20.6                                                  120      5.06            34.8                                                  180      6.66            49.1                                                  240      8.26            63.0                                                  260      9.30            63.0                                                  ______________________________________                                    

The reaction temperature was kept between 80° and 88° C. In the event of excessive reflux, the addition of monomer was reduced. After addition of the monomer, the temperature was increased to 85° to 95° C. for the after-reaction. The dispersions could be packed after cooling to about 35° C.

EXAMPLE 1

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       43.8000                                    Emulsifier                                                                               Nonylphenol-10 EO                                                                             1.0        1.200                                      Buffer    NaHCO.sub.3    0.2        0.240                                      Protective                                                                               PEG 12000      3.0        3.600                                      colloids                                                                       Monomers  Vinyl acetate  18.55      22.260                                               Dibutyl maleate                                                                               33.00      39.600                                     Initiator Potassium persulate                                                                            0.25      0.300                                      solution  Water           7.50      9.000                                      ______________________________________                                         Viscosity:           20,000 mPa.s                                              (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:          clear, very few specks                                    (film/glass)                                                                   Flexibility:         elastic, tack                                             Film/water           resistant                                                 behavior:                                                                      Particle size:                                                                 Solids content:      55.8%                                                     Dispersion adjusted to 53% solids:                                             Viscosity:           5,100 mPa.s                                               (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Solids content:      52.8%                                                     Shear stability:     very good                                                 ______________________________________                                    

EXAMPLE 2

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             0.5        0.005                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Protective                                                                               PEG 12000      3.0        0.030                                      colloid                                                                        Monomer   Vinyl acetate  18.72      0.1872                                               Dibutyl maleate                                                                               33.31      0.3331                                     Initiator Potassium persulfate                                                                           0.25      0.0025                                     solution  Water           7.50      0.0750                                     ______________________________________                                         Viscosity:          3,000 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, some specks                                         (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      430 nm                                                     Solids content:     55.6%                                                      Shear stability:    good                                                       ______________________________________                                    

EXAMPLE 3

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             0.5        0.005                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Protective                                                                               PEG 12000      3.5        0.035                                      colloid                                                                        Monomer   Vinyl acetate  18.56      0.1856                                               Dibutyl maleate                                                                               32.99      0.3299                                     Initiator Potassium persulfate                                                                           0.25      0.0025                                     solution  Water           7.50      0.0750                                     ______________________________________                                         Viscosity:          9,600 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, some specks                                         (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      480 nm                                                     Solids content:     55.2%                                                      Shear stability:    good                                                       ______________________________________                                    

EXAMPLE 4

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             0.5        0.005                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Protective                                                                               PEG 12000      4.0        0.040                                      colloid                                                                        Monomer   Vinyl acetate  18.38      0.1838                                               Dibutyl maleate                                                                               32.67      0.3267                                     Initiator Potassium persulfate                                                                           0.25      0.0025                                     solution  Water           7.50      0.0750                                     ______________________________________                                         Viscosity:          23,500 mPa.s                                               (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, some specks                                         (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      350 mm                                                     Solids content:     55.4%                                                      Shear stability:    good                                                       ______________________________________                                    

EXAMPLE 5

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             1.0        0.010                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Protective                                                                               PEG 12000      3.5        0.035                                      colloid                                                                        Monomer   Vinyl acetate  18.38      0.1838                                               Dibutyl maleate                                                                               32.67      0.3267                                     Initiator Potassium persulfate                                                                           0.25      0.0025                                     solution  Water           7.50      0.0750                                     ______________________________________                                         Viscosity:          20,000 mPa.s                                               (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, some specks                                         (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      334 nm                                                     Solids content:     55.7%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 6

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             1.0        0.010                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Protective                                                                               PEG 12000      4.0        0.040                                      colloid                                                                        Monomer   Vinyl acetate  18.20      0.1820                                               Dibutyl maleate                                                                               32.35      0.3235                                     Initiator Potassium persulfate                                                                           0.25      0.0025                                     solution  Water           7.50      0.0750                                     ______________________________________                                         Viscosity:          28,000 mPa.s                                               (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      337 nm                                                     Solids content:     55.4%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 7

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             1.0        0.010                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Foam inhibitor                                                                           Silicone oil   0.2        0.002                                      Protective                                                                               PEG 12000      3.0        0.030                                      colloid                                                                        Monomer   Vinyl acetate  18.48       0.1848                                              Dibutyl maleate                                                                               32.87       0.3287                                    Initiator Potassium persulfate                                                                           0.25       0.0025                                    solution  Water           7.50       0.0750                                    ______________________________________                                         Viscosity:          3,200 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      470 nm                                                     Solids content:     54.6%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 8

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             1.0        0.010                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Foam inhibitor                                                                           Silicone oil   0.2        0.002                                      Protective                                                                               PEG 5000/6000  3.0        0.030                                      colloid                                                                        Monomer   Vinyl acetate  18.48       0.1848                                              Dibutyl maleate                                                                               32.87       0.3287                                    Initiator Potassium persulfate                                                                           0.25       0.0025                                    solution  Water           7.50       0.0750                                    ______________________________________                                         Viscosity:          250 mPa.s                                                  (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, many specks                                         (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      675 nm                                                     Solids content:     56.6%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 9

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             0.5        0.005                                                Nonylphenol-30 EO                                                                             0.5        0.005                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Foam inhibitor                                                                           Silicone oil   0.2        0.002                                      Protective                                                                               PEG 5000/6000  3.0        0.030                                      colloids                                                                       Monomers  Vinyl acetate  18.48       0.1848                                              Dibutyl maleate                                                                               32.87       0.3287                                    Initiator Potassium persulfate                                                                           0.25       0.0025                                    solution  Water           7.50       0.0750                                    ______________________________________                                         Viscosity:          300 mPa.s                                                  (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      563 nm                                                     Solids content:     52.2%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 10

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO-                                                                            1.0        0.0333                                               sulfate                                                              Buffer    NaHCO.sub.3    0.2        0.002                                      Foam inhibitor                                                                           Silicone oil   0.2        0.002                                      Protective                                                                               PEG 5000/6000  3.0        0.030                                      colloid                                                                        Monomer   Vinyl acetate  18.48      0.1848                                               Dibutyl maleate                                                                               32.87      0.3287                                     Initiator Potassium persulfate                                                                          0.25       0.0025                                     solution  Water          7.50       0.0750                                     ______________________________________                                         Viscosity:        7,600 mPa.s                                                  (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:       clear, very few specks                                       (film/glass)                                                                   Flexibility:      elastic, tack                                                Film/water        resistant                                                    behavior:                                                                      Particle size:    250 nm                                                       Solids content:   56.0%                                                        Shear stability:  poor, skin formation                                         ______________________________________                                    

EXAMPLE 11

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             1.0        0.010                                                sulfate                                                              Buffer    NaHCO.sub.3    0.2        0.002                                      Foam inhibitor                                                                           Silicone oil   0.2        0.002                                      Protective                                                                               PEG 5000/6000  3.0        0.030                                      colloid                                                                        Monomer   Vinyl acetate  18.48      0.1848                                               Dibutyl maleate                                                                               32.87      0.3287                                     Initiator Potassium persulfate                                                                          0.25       0.0025                                     solution  Water          7.50       0.0750                                     ______________________________________                                         Viscosity:          250 mPa.s                                                  (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      385 nm                                                     Solids content:     53.4%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 12

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             1.0        0.010                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Foam inhibitor                                                                           Silicone oil   0.2        0.002                                      Protective                                                                               PEG 20000      3.0        0.030                                      colloid                                                                        Monomer   Vinyl acetate  18.48      0.1848                                               Dibutyl maleate                                                                               32.87      0.3287                                     Initiator Potassium persulfate                                                                          0.25       0.0025                                     solution  Water          7.50       0.0750                                     ______________________________________                                         Viscosity:          16,000 mPa.s                                               (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      1,870 nm                                                   Solids content:     51.8%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 13

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    36.5       0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                             1.0        0.010                                      Buffer    NaHCO.sub.3    0.2        0.002                                      Foam inhibitor                                                                           Silicone oil   0.2        0.002                                      Protective                                                                               PEG 50000      3.0        0.030                                      colloid                                                                        Monomer   Vinyl acetate  18.48      0.1848                                               Dibutyl maleate                                                                               32.87      0.3287                                     Initiator Potassium persulfate                                                                          0.25       0.0025                                     solution  Water          7.50       0.0750                                     ______________________________________                                         Viscosity:          10,000 mPa.s                                               (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic, tack                                              Film/water          resistant                                                  behavior:                                                                      Particle size:      1,500 nm                                                   Solids content:     53.4%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 14

    ______________________________________                                         Raw material         Concentration                                             type      Raw material   % by weight                                                                               Kg                                         ______________________________________                                         Water                    34.17      10.251                                     Emulsifier                                                                               Nonylphenol-10 EO-                                                                            1.0        0.999                                      Buffer    NaHCO.sub.3    0.2        0.060                                      Foam inhibitor                                                                           Silicone oil   0.2        0.060                                      Protective                                                                               PEG 12000      3.5        1.050                                      colloid                                                                        Monomer   Vinyl acetate  33.56      10.068                                               Dibutyl maleate                                                                               17.29      5.187                                      Initiator Potassium persulfate                                                                          0.25       0.075                                      solution  Water          7.50       2.250                                      ______________________________________                                         Viscosity:        12,000 mPa.s                                                 (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:       clear, very few specks                                       (film/glass)                                                                   Flexibility:      elastic                                                      Film/water        resistant                                                    behavior:                                                                      Particle size:    450 nm                                                       Solids content:   55.8%                                                        ______________________________________                                    

EXAMPLE 15

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   42.5        0.425                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            0.5         0.005                                      Buffer    NaHCO.sub.3   0.2         0.002                                      Protective                                                                               PEG 12000     5.0         0.050                                      colloid                                                                        Monomer   Vinyl acetate 44.05       0.4405                                     Initiator Potassium persulfate                                                                         0.25        0.0025                                     solution  Water         7.50        0.0750                                     ______________________________________                                         Viscosity:          2,800 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, no specks                                           (film/glass)                                                                   Flexibility:        brittle, elastic                                           Film/water          resistant                                                  behavior:                                                                      Particle size:      280 nm                                                     Solids content:     49.8%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 16

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   42.5        0.425                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            0.5         0.005                                      Buffer    NaHCO.sub.3   0.2         0.002                                      Protective                                                                               PEG 12000     7.0         0.070                                      colloid                                                                        Monomer   Vinyl acetate 44.05       0.4205                                     Initiator Potassium persulfate                                                                         0.25        0.0025                                     solution  Water         7.50        0.0750                                     ______________________________________                                         Viscosity:          3,500 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, no specks                                           (film/glass)                                                                   Flexibility:        elastic                                                    Film/water          resistant                                                  behavior:                                                                      Particle size:      230 nm                                                     Solids content:     49.8%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 17

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   42.5        0.425                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            0.5         0.005                                      Buffer    NaHCO.sub.3   0.2         0.002                                      Protective                                                                               PEG 12000     10.0        0.100                                      colloid                                                                        Monomer   Vinyl acetate 39.05       0.3905                                     Initiator Potassium persulfate                                                                         0.25        0.0025                                     solution  Water         7.50        0.0750                                     ______________________________________                                         Viscosity:          3,800 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, no specks                                           (film/glass)                                                                   Flexibility:        elastic                                                    Film/water          resistant                                                  behavior:                                                                      Particle size:      220 nm                                                     Solids content:     49.6%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 18

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   42.5        0.425                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            1.0         0.010                                      Buffer    NaHCO.sub.3   0.2         0.002                                      Protective                                                                               PEG 12000     5.0         0.050                                      colloid                                                                        Monomer   Vinyl acetate 43.55       0.4355                                     Initiator Potassium persulfate                                                                         0.25        0.0025                                     solution  Water         7.50        0.0750                                     ______________________________________                                         Viscosity:          5,500 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic                                                    Film/water          resistant                                                  behavior:                                                                      Particle size:      210 nm                                                     Solids content:     49.2%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 19

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   42.5        0.425                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            1.0         0.010                                      Buffer    NaHCO.sub.3   0.2         0.002                                      Protective                                                                               PEG 12000     7.0         0.070                                      colloid                                                                        Monomer   Vinyl acetate 41.55       0.4155                                     Initiator Potassium persulfate                                                                         0.25        0.0025                                     solution  Water         7.50        0.0750                                     ______________________________________                                         Viscosity:          5,200 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic                                                    Film/water          resistant                                                  behavior:                                                                      Particle size:      240 nm                                                     Solids content:     49.4%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 20

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   42.5        0.425                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            1.0         0.010                                      Buffer    NaHCO.sub.3   0.2         0.002                                      Protective                                                                               PEG 12000     10.0        0.100                                      colloid                                                                        Monomer   Vinyl acetate 38.55       0.3855                                     Initiator Potassium persulfate                                                                         0.25        0.0025                                     solution  Water         7.50        0.0750                                     ______________________________________                                         Viscosity:          3,400 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic                                                    Film/water          resistant                                                  behavior:                                                                      Particle size:      200 nm                                                     Solids content:     49.6%                                                      Shear stability:    very good                                                  ______________________________________                                    

EXAMPLE 21

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   42.5        0.425                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            0.25         0.0025                                    Buffer    NaHCO.sub.3   0.2         0.002                                      Protective                                                                               PEG 12000     5.0         0.050                                      colloid                                                                        Monomer   Vinyl acetate 44.3        0.443                                      Initiator Potassium persulfate                                                                         0.25         0.0025                                    solution  Water         7.50         0.0750                                    ______________________________________                                         Viscosity:         550 mPa.s                                                   (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:        clear, few specks                                           (film/glass)                                                                   Flexibility:       elastic                                                     Film/water         resistant                                                   behavior:                                                                      Particle size:     200 nm                                                      Solids content:    49.9%                                                       Shear stability:   very good                                                   ______________________________________                                    

EXAMPLE 22

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   42.5        0.425                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            0.25         0.0025                                    Buffer    NaHCO.sub.3   0.2         0.002                                      Protective                                                                               PEG 12000     7.0         0.070                                      colloid                                                                        Monomer   Vinyl acetate 42.3        0.423                                      Initiator Potassium persulfate                                                                         0.25         0.0025                                    solution  Water         7.50         0.0075                                    ______________________________________                                         Viscosity:         950 mPa.s                                                   (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:        clear, few specks                                           (film/glass)                                                                   Flexibility:       elastic                                                     Film/water         resistant                                                   behavior:                                                                      Particle size:     195 nm                                                      Solids content:    50.4%                                                       Shear stability:   very good                                                   ______________________________________                                    

EXAMPLE 23

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   42.5        0.425                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            0.25        0.0025                                     Buffer    NaHCO.sub.3   0.2         0.002                                      Protective                                                                               PEG 12000     10.0        0.100                                      colloid                                                                        Monomer   Vinyl acetate 39.3        0.393                                      Initiator Potassium persulfate                                                                         0.25        0.0025                                     solution  Water         7.50        0.0075                                     ______________________________________                                         Viscosity:          2,500 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:         clear, few specks                                          (film/glass)                                                                   Flexibility:        elastic                                                    Film/water          resistant                                                  behavior:                                                                      Particle size:      205 nm                                                     Solids content:     50.2%                                                      Shear stability:    very good                                                  ______________________________________                                    

COMPARISON EXAMPLE 1

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   36.5        0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            0.3         0.010                                                sulfate                                                              Buffer    NaHCO.sub.3   0.2         0.002                                      Foam inhibitor                                                                           Silicone oil  0.2         0.002                                      Protective                                                                               Mowiol 4/88*  1.95        0.0195                                     colloid   Mowiol 18/88* 1.00        0.0100                                     Monomer   Vinyl acetate 18.834       0.18834                                             Dibutyl maleate                                                                              33.314       0.33314                                   Initiator Potassium persulfate                                                                         0.25        0.0025                                     solution  Water         7.50        0.0750                                     ______________________________________                                         Viscosity:           20,000 mPa.s                                              (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:          clear                                                     (film/glass)                                                                   Flexibility:         elastic                                                   Film/water           resistant                                                 behavior:                                                                      Particle size:       1020 nm                                                   Solids content:      55.4%                                                     Shear stability:     poor                                                      ______________________________________                                          *Polyvinyl alcohol, products of HOECHST AG                               

COMPARISON EXAMPLE 2 AND 2.1

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   35.8        0.358                                      Emulsifier                                                                               Nonylphenol-10 E0                                                                            0.3         0.010                                                sulfate                                                              Buffer    NaHCO.sub.3   0.2         0.002                                      Foam inhibitor                                                                           Silicone oil  0.1         0.001                                      Protective                                                                               Mowiol 4/88*  2.95         0.0295                                    colloid                                                                        Monomer   Vinyl acetate 18.834       0.18834                                             Dibutyl maleate                                                                              33.314       0.33314                                   Initiator Potassium persulfate                                                                         0.3         0.003                                      solution  Water         7.5          0.0750                                    ______________________________________                                         Viscosity:        16,000 mPa.s                                                 (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:       clear, very few specks                                       (film/glass)                                                                   Flexibility:      elastic                                                      Film/water        resistant                                                    behavior:                                                                      Particle size:    920 nm                                                       Solids content:   56.1%                                                        ______________________________________                                          Polyvinyl alcohol, product of HOECHST AG                                 

In Comparison Example 2.1, 3% by weight PEG12000 was subsequently added to the emulsion polymer

COMPARISON EXAMPLE 3

    ______________________________________                                         Raw material         Concentration                                             type       Raw material  % by weight Kg                                        ______________________________________                                         Water                    36.5        0.365                                     Emulsifier Nonylphenol-10 E0                                                                            0.3         0.010                                                sulfate                                                             Buffer     NaHCO.sub.3   0.2         0.002                                     Foam inhibitor                                                                            Silicone oil  0.2         0.002                                     Protective Mowiol 4/88*  1.95        0.0195                                    colloid    Mowiol 18/88* 1.00        0.0100                                    Monomer    Vinyl acetate 21.50       0.2150                                               Dibutyl maleate                                                                              30.67       0.3067                                    Initiator  Potassium persulfate                                                                         0.25        0.0025                                    solution   Water         7.50        0.0750                                    ______________________________________                                         Viscosity:           23,000 mPa.s                                              (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:          clear                                                     (film/glass)                                                                   Flexibility:         elastic                                                   Film/water           resistant                                                 behavior:                                                                      Particle size:       808 nm                                                    Solids content:      55.8%                                                     Shear stability:     poor                                                      ______________________________________                                          *Polyvinyl alcohol, products of HOECHST AG                               

COMPARISON EXAMPLE 4

    ______________________________________                                         Raw material        Concentration                                              type      Raw material  % by weight Kg                                         ______________________________________                                         Water                   36.5        0.365                                      Emulsifier                                                                               Nonylphenol-10 EO                                                                            0.3         0.010                                                sulfate                                                              Buffer    NaHCO.sub.3   0.2         0.002                                      Foam inhibitor                                                                           Silicone oil  0.2         0.002                                      Protective                                                                               Mowiol 4/88*  1.95        0.0195                                     colloid   Mowiol 18/88* 1.00        0.0100                                     Monomer   Vinyl acetate 26.075       0.26075                                             Dibutyl maleate                                                                              26.075       0.26075                                   Initiator Potassium persulfate                                                                         0.25        0.0025                                     solution  Water         7.50        0.0750                                     ______________________________________                                         Viscosity:           27,500 mPa.s                                              (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:          clear                                                     (film/glass)                                                                   Flexibility:         elastic                                                   Film/water           resistant                                                 behavior:                                                                      Particle size:       627 nm                                                    Solids content:      55.7%                                                     Shear stability:     poor                                                      ______________________________________                                          Polyvinyl alcohol, products of HOECHST AG                                

COMPARISON EXAMPLE 5

    ______________________________________                                         Raw material         Concentration                                             type       Raw material  % by weight Kg                                        ______________________________________                                         Water                    35.8        0.358                                     Emulsifier Nonylphenol-10 EO                                                                            0.3         0.010                                                sulfate                                                             Buffer     NaHCO.sub.3   0.2         0.002                                     Foam inhibitor                                                                            Silicone oil  0.1         0.001                                     Protective Mowiol 18/88* 2.95        0.0295                                    colloid                                                                        Monomer    Vinyl acetate 21.50       0.2150                                               Dibutyl maleate                                                                              30.67       0.3067                                    Initiator  Potassium persulfate                                                                         0.30        0.0030                                    solution   Water         7.50        0.0750                                    ______________________________________                                         Viscosity:           155,000 mPa.s                                             (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:          clear                                                     (film/glass)                                                                   Flexibility:         soft - elastic                                            Film/water           resistant                                                 behavior:                                                                      Particle size:       680 nm                                                    Solids content:      55.9%                                                     Shear stability:     poor                                                      ______________________________________                                          *Polyvinyl alcohol, products of HOECHST AG                               

COMPARISON EXAMPLE 6 AND 6.1

    ______________________________________                                         Raw material         Concentration                                             type       Raw material  % by weight Kg                                        ______________________________________                                         Water                    35.35       0.3535                                    Emulsifier Nonylphenol-10 EO                                                                            0.50        0.0165                                               sulfate                                                             Buffer     NaHCO.sub.3   0.20        0.0020                                    Foam inhibitor                                                                            Silicone oil  0.10        0.0010                                    Protective Mowiol 18/88* 6.00        0.0600                                    colloid                                                                        Monomer    Vinyl acetate 32.30       0.3230                                               Dibutyl maleate                                                                              16.65       0.1665                                    Initiator  Potassium persulfate                                                                         0.25        0.0025                                    solution   Water         7.50        0.0750                                    ______________________________________                                         Viscosity:         162,000 mPa.s                                               (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:        clear, few specks                                           (film/glass)                                                                   Flexibility:       elastic                                                     Film/water         resistant                                                   behavior:                                                                      Particle size:     --                                                          Solids content:    53.8%                                                       ______________________________________                                          *Polyvinyl alcohol, products of HOECHST AG                               

Comparison Example 6.1 contains 3.5% by weight subsequently added PEG 12000

COMPARISON EXAMPLE 7 AND 7.1

    ______________________________________                                         Raw material         Concentration                                             type       Raw material  % by weight Kg                                        ______________________________________                                         Water                    35.3        10.500                                    Emulsifier Nonylphenol-10 EO                                                                            0.5         0.495                                                sulfate                                                             Buffer     NaHCO.sub.3   0.2         0.060                                     Foam inhibitor                                                                            Silicone oil  0.1         0.030                                     Protective CMC/A 400 P*  2.5         0.75                                      Colliod                                                                        Monomer    Vinyl acetate 34.5        10.350                                               Dibutyl maleate                                                                              18.0        5.400                                     Initiator  Potassium persulfate                                                                         0.25        0.075                                     solution   Water         7.50        2.250                                     ______________________________________                                         Viscosity:         10,000 mPa.s                                                (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:        clear, few specks                                           (film/glass)                                                                   Flexibility:       elastic                                                     Film/water         redispersible                                               behavior:                                                                      Particle size:     930 nm                                                      Solids content:    56.1%                                                       ______________________________________                                          *Polyvinyl alcohol, product of HOECHST AG                                

Comparision Example 7.1 contains 3.5% by weight subsequently added PEG 12000

COMPARISON EXAMPLE 8 AND 8.1

The commercially available dispersion "Mowilith D 50" (a product of Hoechst AG) is used as Comparison Example 8.

In comparison Example 8.1, 5.0% by weight PEG 12000 is added to this dispersion. The commercially available dispersion contains a vinyl acetate polymer for a solids concentration of 50% by weight (protective colloid: approx. 3.0% by weight polyvinyl alcohol).

COMPARISON EXAMPLE 9 AND 9.1

    ______________________________________                                         Raw material         Concentration                                             type       Raw material  % by weight Kg                                        ______________________________________                                         Water                    36.43       10.239                                    Emulsifier Nonylphenol-10 EO                                                                            1.0         0.999                                                sulfate                                                             Buffer     NaHCO.sub.3   0.2         0.060                                     Foam inhibitor                                                                            Silicone oil  0.1         0.030                                     Protective CMC/A 400 P*  5.0         1.500                                     colloid                                                                        Monomer    Vinyl acetate 49.50       14.850                                    Initiator  Potassium persulfate                                                                         0.25        0.075                                     solution   Water         7.50        2.250                                     ______________________________________                                         Viscosity:       37,500 mPa.s                                                  (Brookfield RVT                                                                20° C./20 r.p.m.)                                                       Appearance:      slightly cloudy, few specks                                   (film/glass)                                                                   Flexibility:     brittle                                                       Film/water       redispersible                                                 behavior:                                                                      Particle size:   1450 nm                                                       Solids content:  56.4%                                                         ______________________________________                                          *Polyvinyl alcohol, product of HOECHST AG                                

Comparison Example 9.1 contains 5.0% by weight subsequently added PEG 12000

Feel assessment

The dispersions of Examples 1 to 9 and 11 to 15 and of Comparison Examples 1, 2, 2.1 and 6 to 9.1 are applied to cotton fabric using a laboratory padder and dried on a tenter frame for 60 seconds at 130° C. The liquor concentrations are adjusted to give a solids covering of 4%. Feel was then assessed on the following scale:

Feel:

1=very hard

8=very soft

Volume:

1=very flat

5=very full

The feel marks awarded to the samples tested are shown in the following Table. The shear stability of the materials of Comparison Examples 3 to 5 is poor.

                  TABLE                                                            ______________________________________                                                           Feel assessment                                                                feel  volume                                                 ______________________________________                                         Example                                                                        1                   8       5                                                  2                   8       5                                                  3                   8       5                                                  4                   8       5                                                  5                   8       5                                                  6                   8       5                                                  7                   8       5                                                  8                   8       5                                                  9                   8       5                                                  10                  8       5                                                  11                  8       5                                                  12                  8       5                                                  13                  8       5                                                  14                  5       3                                                  15                  5       1                                                  Comparison Example 1                                                                               6       5                                                  Comparison Example 2                                                                               6       5                                                    Comparison Example 2.1                                                                           6-7     5                                                  Comparison Example 6                                                                               2       3                                                    Comparison Example 6.1                                                                           3       3                                                  Comparison Example 7                                                                               2-3     3                                                    Comparison Example 7.1                                                                           3-4     3                                                  Comparison Example 8                                                                               1       1                                                    Comparison Example 8.1                                                                           1-2     1                                                  Comparison Example 9                                                                               2       1                                                    Comparison Example 9.1                                                                           3       1                                                  ______________________________________                                     

We claim:
 1. In a method of treating textiles with an aqueous emulsion polymer, the improvement wherein the textile is treated with an aqueous emulsion comprising:(a) from about 40 to about 60% by weight of either a polymer of vinyl acetate, a copolymer of vinyl acetate and dibutyl maleate, or a mixture of the foregoing; and (b) from about 2 to about 10% by weight of a polyethylene glycol having a molecular weight of from about 3,000 to about 50,000;wherein the above percentages by weight are based on the weight of the aqueous emulsion, and wherein the aqueous emulsion is employed in a quantity sufficient to impart a soft and full feel to the textile.
 2. The method of claim 1 wherein the textile is in sheet form.
 3. The method of claim 1 wherein the average molecular weight of the polyethylene glycol is from about 8,000 to about 25,000.
 4. The method of claim 1 wherein at least part of the polyethylene glycol was present during the preparation of the aqueous emulsion.
 5. The method of claim 1 wherein from about 3 to about 10% of component (b) is present in the aqueous emulsion.
 6. The method of claim 1 wherein a component (a) is a copolymer of vinyl acetate and dibutyl maleate having a dibutyl maleate content of from about 5 to about 45 mole %, based on the total of vinyl acetate and dibutyl maleate.
 7. The method of claim 1 wherein the aqueous emulsion also contains from about 0.5 to about 5% of an emulsifier.
 8. The method of claim 7 wherein from about 0.5 to about 3% of the emulsifier is present in the aqueous emulsion.
 9. The method of claim 7 wherein from about 0.5 to about 2% of the emulsifier is present in the aqueous emulsion.
 10. The method of claim 7 wherein the emulsifier is a nonionic surfactant.
 11. The method of claim 10 wherein the nonionic surfactant is a polyethylene oxide adduct with a hydrocarbon compound containing a reactive hydrogen atom.
 12. The method of claim 10 wherein the nonionic surfactant is an alkylphenol ethylene oxide adduct.
 13. The method of claim 10 wherein the nonionic surfactant is nonylphenol.10ethylene oxide units. 